Plasticized polyvinyl halides



Patented Aug. 7, 1951 UNITED STATES PATENT OFFICE PLASTICIZED POLYVINYLHALIDIS No Drawing. Application August 21, 1950. Serial No. 180,689

1 Claims. 1

This invention relates to compositions comprising polymers of vinylhalides and relates more particularly to compositions comprising vinylchloride polymers plasticized with esters of(1',2-dicarboxyethyl)octadecenoic acid.

A wide variety of plasticizers has been employed for the purpose ofimproving the physical properties of vinyl chloride polymers. Particularattention has been given to the improvement of flexibility and heat andlight stability of such plasticlzed compositions. In many instances theimprovement in flexibility has been obtainable only by sacrificin otherdesirable properties of an ideal polyvinyl chloride composition, such aslow volatility, color and heat stability, water absorption, etc.

Now I have found that very good flexibility, without sacrifice oftemperature stability and very low volatility, is imparted to vinylchloride polymers when there is employed with the polymers an allylester of (1',2'-dicarboxyethyl) octadecenoic acid. Esters of this typeare broadly disclosed in the Clocker Patent U. S. No. 2,188,888, and inthe article by Ross, Gebhart and Gerecht, appearing in the Journal ofthe American Chemical Society, 68 1373 (1946). Briefly, they areobtainable by the addition reaction of maleic anhydride with oleic acidor its esters and subsequent esteriflcatlon. While isomeric products arepossible, and the position at which the anhydride residue is attached tothe oleic compound is not known, the reaction of oleic acid or of analkyl oleate with maleic anhydride proceeds probably according to thescheme;

cuiwmhcmcmcmhcoon CHC:\

CH|(CH:),CH.CH:CH(CH:)n-CO0R HC:O

o Ell-C14) wherein a: is a whole number between 5 and 8 and R is amember of the group consisting of hydrogen. alkyl radicals of from 1 to6 carbon atoms, and the allyl radical.

Esteriflcation of the resulting adduct with allyl alcohol yields thetrialkyl ester which probably has the structure:

in which R is the allyl radical, Z is selected from the class consistingof R and alkyl radicals of from 1 to 6 carbon atoms and :r is a wholenumber between 5 and 8.

Because of uncertainty concerning the position at which the maleicresidue is attached to the oleic group the present esters will behereinafter referred to without stipulating the position of the(1,2'-dicarboxyethyl) group.

As examples of compounds having the above general formula may bementioned triallyl (1',2'- dicarboxyethyl)octadecenoate, and the alkyl[1,2' bis(carboallyloxy) ethylloctadecenoates in which the alkyl grouphas from 1 to 6 carbon atoms, e. g., methyl [1,2' bis carboallyloxy)ethyiloctadecenoate, lsopropyl[1',2'-bis-(carboallyloxy)ethylloctadecenoate, amyl [1',2'-bis-(carboallyloxy)ethylloctadecenoate and 2-ethylbutyl [1,2'bis(carboallyloxy) ethylloctadec enoate.

Triallyl (l,2' dicarboxyethylloctadecenoate and alkyl [1,2'bis(carboallyloxy)ethylloctadecenoates in which the alkyl radical hasfrom 1 to 6 carbon atoms are valuable plasticizers for polyvinylchloride and oopolymers of at least '70 per cent by weight of vinylchloride and up to 30 per cent by weight of an unsaturated monomercopolymerized therewith, for example vinyl acetate, vinylidene chloride,etc.

Adducts of acyclic oleilnic acids and longchained unsaturated acids havebeen hitherto generally suggested for use as softening agents. I havefound, however, that triallyl (1',2'-dicarboxyethyhoctadecenoate andalkyl [1',2'-bis- (carboallyloxy)ethylloctadecenoates are of outstandingvalue as plasticizers, these esters serving not only to soften vinylchloride polymers, but also to impart simultaneously a high degree oflow temperature flexibility, very good temperature stability and greatmechanical strength to these polymers. While many of the estersencompassed by the Clocker patent referred to above are incompatiblewith polymers and copolymers of vinyl chloride and do not givecontinuous, homogeneous compositions, the present allyl esters arecompatible with vinyl chloride polymers and show no exudation ofplasticizer even at plasticizer content of up to 50 per cent. Althoughthe quantity of plasticizer will depend upon the particular polymer tobe plasticized and upon its molecular weight. it is generally found thatcompositions having from 5 per cent to 50 per cent by weight ofplasticizer will, in most cases, be satisfactory for general utility.The good flexibility of the plasticized compositions increases withincreasing plasticizer concentration.

In evaluating plasticizer emciency use is made of the followingempirical testing procedures:

Compatibility.Visual inspection of the plasti- 3 cimdccmpositionismloyminccmpatihllityod the plasticiser with the polymer being demonstratedby cloudinfls and exudation oi the Hardness.-A standard instrument madeby the fihorelnsh'umentoompanyisusedi'orthisdetermination and M- w a thehardness in units from 1 to 100. Thehardnessoiacompositionis judged byits resistance to the penetration of a standard needle applied to thecomposition under a standard load for a standard length of time.

Low temperature flexibilitm-Iow temperature flexibility is one of themost important properties oi elastomeric vinyl compositions. While manyplasticizers will produce flexible compositions at room temperature theflexibility or these compositions at low temperatures may varyconsiderably, i. e., plasticized polyvinyl chloride compositions thatare flexible at room temperature often become very brittle and uselessat low temperatures. Low temperature flexibility tests herein employedare according to the Clash-Berg method. This method determines thetorsional flexibility of a plastic at various temperatures. Thetemperature at which the vinyl composition exhibits an arbitrarilyestablished minimum flexibility is defined as the Low TemperatureFlexibility of the composition. This value may also be defined as thelower temperature limit of the plasticized composition's usefulness asan elastomer.

Volotflitu.-Just as a decrease in low temperature often results indecreased flexibility of a plasticized polymer composition so does adecrease in plasticiser concentration when caused by volatilisation ofthe plasticizer. Hence, plasticizers which are readily volatilized fromthe plasticlaed composition as a result of aging or heating areinefllcient because upon volatilization the plasticiaed compositionsbecome still and hard. The test for plasticizer volatility hereinemployed is that described by the American Society for Testing Materialsunder the designation 13444-441.

Water resistance-The amount oi water absorption and the amount orleaching that takes place when the plasticized composition is immersedin distilled water for 24 hours is determined.

The invention is further illustrated, but not limited. by the followingexample:

Example Sixty parts of polyvinyl chloride and 40 parts by weight of thetriallyl ester oi! (1',2'-dicarboxyethyl) octadecenoic acid were mixedon a rolling mill to a homogeneous blend. During the millins there wasobserved substantially no fuming and discoloration. A molded sheet ofthe mixture was clear and transparent and substantially colorless.Testing oi the molded sheet for low temperature flexibility. accordingto the testing procedure described above. gave a value of minus 45 C.which value denotes extremely good low temperature properties. Tests onthe volatility characteristics oi the plnsticised composition gave avalue or 1.26 per cent which showed very good retention oi plasticinerand indicated good temperature characteristics oi the composition. Thematerialhadaoi'll before thevolatilltytestandaoi'lilai'terthe volatilitytest. when subjected to heat at a tempentureoiflb'llioraperiodoIBOminutesthe clarity and color of the molded product weresubstantially unchanged. Tests oi the water-resistmce properties oi theplacticised material cmare obtained clear, colorless compositions ofvery good flexibility and stability.

While the above example shows only compositions in which the ratio ofplasticizer to polymer content is 40:60, this ratio being employed inorder to get comparable eiiiciencies, the content of ester to polyvinylchloride may be widely varied, depending upon the properties desired inthe iinal product. For many purposes a plasticirer content of, say, fromonly 10 per cent to 20 per cent is preferred. The present esters arecompatible with polyvinyl chloride over wide ranges of concentrations,up to 50 per cent oi ester based on the total weight oi the plasticiscdcomposition yielding desirable products.

Although the invention has been described particularly with reierence tothe use oi the present allyl esters oi(l',2'-dlcarboxyethyl)octadccenoic acid as plasticizers tor polyvinylchloride. these esters are advantageously employed also as plastlcizersi'or copolymers of vinyl chloride, for example, the copolymers of vinylchloride with vinyl acetate. vinylidene chloride. etc. Preferably. suchcopolymers have a high vinyl chloride content, i. e., a vinyl chloridecontent of at least '70 per cent by weight or vinyl chloride and up to30 per cent by weight 01' the copolymerizable monomer.

The plasticized polyvinyl halide compositions of the present inventionhave good thermal stability; however. for many purposes it may beadvantageous to use known stabilizers in the plasticized compositions.Inasmuch as the present esters are substantially unreactive with thecommercially available heat and light stabilisers which are commonlyemployed with P lyvinyl chloride or copolymers thereof, the presence oisuchmaterialsintheplssticisedmaterialsdoes not impair the valuableproperties of the present esters. The present esters are oi generalutility in softening vinyl chloride polymers. They may be used as theonly plasticising component in a compounded vinyl chloride polymer orthey may be used in conjunction with other plasticizers.

What I claim is:

l. A resinous composition comprising a vinyl chloride polymerplasticised with an ester selected from the class consisting of triallyl(l',2'-dicarboxyethylloctadccemate and alkyl[1'.2'-biscarboallyloxynthylloctadecenoatcs in which thealkylradicalhastromltodcarbonatom.

2. A resinous composition comprising polyvinyl chloride plasticised withan ester selected from the class consisting of triallyl(1'.2'-dicarboxyethyboctadccenoate and alkyl[l'.2'-bis(carboallyloxyiethylltcs in which the alkyl radical has from 1to 6 carbon atoms.

3. A resinous composition comprising polyvinyl chloride plasticised withan ester selected from the class consisting of triallyl(l',2'-dicarboxyl6 cthylitc and alkyl [l'.2'-bis(carboaliyloxy)ethylloctadecenoates in which the alkyl radical has from 1 to 6 carbonatoms. said ester being from 5 to 50 per cent of the weight of thecomposition.

4. A resinous composition comprising a. copolymer of at least '10 percent by weight of vinyl chloride and up to 30 per cent by weight of anunsaturated monomer copolymerizable therewith, said copolymer beingplasticized with an ester selected from the class consisting of triallyl(1',2'- dioarboxyethyl)octadecenoate and alkyl [1',2'- bis(carboalyloxy) ethyl] octadecenoates in which the alkyl radical has from1 to 6 carbon atoms.

5. A resinous composition comprising a copolymer of at least 70 per centby weight of vinyl chloride and up to 30 per cent by weight 01 anunsaturated monomer copolymerizable therewith, said copolymer beingplasticized with an ester selected from the class consisting of triallyl(1',2'-dicarboxyethy1)octadecenoate and alkyl 1 ',2 -bls(carboally1oxy)ethyl1octadecenoates in which the alkyl radical has from 1 to 6 carbonatoms, said ester being from 5 to 50 per cent of the weight of thecomposition.

6. A resinous composition comprising po1y vinyl chloride plasticizedwith triallyl (1',2'-dioarboxyethyl) octadecenoate.

7. A resinous composition comprising polyvinyl chloride plasticized withtriallyl (1',2'-dicarbonv ethyDoctadecenoate. said ester being from 5 to50 per cent of the weight of the composition.

JOACHIM DAZZI.

No references cited.

Certificate of Correction Patent No. 2,563,312

August 7, 1951 J OACHIM DAZZI It is hereby certified that error appearsin the printed specification of the above numbered patent requiringcorrection as follows:

Column 5, line 12, for bis(carboalyloxy) ethyl] read bis(carboalZ3l0a:y)

ethyl] and that the said Letters Patent should be read as correctedabove, so that the same may conform to the record of the case in thePatent Oifice.

Signed and sealed this 30th day of October, A. D. 1951.

THOMAS F. MURPHY,

Assistant Gammiuioner of Patent:-

aliyloxy) ethylloctadecenoates in which the alkyl radical has from 1 to6 carbon atoms. said ester being from 5 to 50 per cent of the weight ofthe composition.

4. A resinous composition comprising a. copolymer of at least '10 percent by weight of vinyl chloride and up to 30 per cent by weight of anunsaturated monomer copolymerizable therewith, said copolymer beingplasticized with an ester selected from the class consisting of triallyl(1',2'- dioarboxyethyl)octadecenoate and alkyl [1',2'- bis(carboalyloxy) ethyl] octadecenoates in which the alkyl radical has from1 to 6 carbon atoms.

5. A resinous composition comprising a copolymer of at least 70 per centby weight of vinyl chloride and up to 30 per cent by weight 01 anunsaturated monomer copolymerizable therewith, said copolymer beingplasticized with an ester selected from the class consisting of triallyl(1',2'-dicarboxyethy1)octadecenoate and alkyl 1 ',2 -bls(carboally1oxy)ethyl1octadecenoates in which the alkyl radical has from 1 to 6 carbonatoms, said ester being from 5 to 50 per cent of the weight of thecomposition.

6. A resinous composition comprising po1y vinyl chloride plasticizedwith triallyl (1',2'-dioarboxyethyl) octadecenoate.

7. A resinous composition comprising polyvinyl chloride plasticized withtriallyl (1',2'-dicarbonv ethyDoctadecenoate. said ester being from 5 to50 per cent of the weight of the composition.

JOACHIM DAZZI.

No references cited.

Certificate of Correction Patent No. 2,563,312

August 7, 1951 J OACHIM DAZZI It is hereby certified that error appearsin the printed specification of the above numbered patent requiringcorrection as follows:

Column 5, line 12, for bis(carboalyloxy) ethyl] read bis(carboalZ3l0a:y)

ethyl] and that the said Letters Patent should be read as correctedabove, so that the same may conform to the record of the case in thePatent Oifice.

Signed and sealed this 30th day of October, A. D. 1951.

THOMAS F. MURPHY,

Assistant Gammiuioner of Patent:-

1. A RESINOUS COMPOSITION COMPRISING A VINYL CHLORIDE POLYMERPLASTICIZED WITH AN ESTER SELECTED FROM THE CLASS CONSISTING OF TRIALLYL(1'',2''-DICARBOXYETHYL) OCTADECENOATE AND ALKYL(1'',2''-BISCARBOALLYLOXY) ETHYL)OCTADECENOATES IN WHICH THE ALKYLRADICAL HAS FROM 1 TO 6 CARBON ATOMS.